Amine salts of tertiary amino acids

ABSTRACT

Amine salts of tertiary amino acids have been found to be effective as catalysts for polyurethane synthesis and they have been found to exhibit delayed action, in many instances, in the polymerization of urethanes. Typically, the amine salts of tertiary amino acids are formed by initially reacting a primary or secondary amine with an aldehyde and disubstituted acid to form a Mannich adduct and then reacting the resulting Mannich acid adduct with an amine.

BACKGROUND OF THE INVENTION

1. Field

Polyurethanes, which are formed by reacting an isocyanate with areactive hydrogen providing component, such as a polyol, have beenwidely used in preparing rigid and flexible foams, castings, adhesivesand coatings. Typically, the reaction between the isocyanate and thepolyol has been catalyzed by using various components such as amines,e.g. tertiary amines and organometallics, particularly organo tincompounds such as stannous octoate, dibutyl tin laurate, tinethylhexanoate and so forth. The effectiveness of the catalyst is oftenmeasured by the cream time, which is the time required for theisocyanate and polyol syrup to turn from a clear solution to a creamycolor; the gel time, which is the time required for polymer particles toform in the syrup; rise time, which is the time required for the syrupto rise to its maximum height; and cure time which is the time to reacha tack-free state.

In some applications for polyurethanes it is desirable to effectreaction in the shortest time possible and, therefore, pg,2 catalystshaving tremendous activity are desired. In some applications, though, asin the molding of intricate parts or large objects, it may be desirableto keep the polyurethane composition in a fluid state for an extendedtime to permit the composition to completely fill the mold or flow intothe cracks and crevices of the mold. Then, once the mold is completelyfilled, it is desirable to effect polymerization of the polyurethane inthe shortest time possible so that the finished parts can be removed andthe mold recharged with new materials. In this regard, it is desirableto delay the initial reaction, but after reaction commences thencatalyze the polymerization rate. To do this it is necessary to extendthe cream time to permit the polyurethane composition to penetrate thecracks and crevices in the mold and to extend the gelation time as thepolyurethane foam on gelling becomes intractable and resists molding.However, once the reaction begins, it is desirable to end up with a riseand cure time comparable to those achieved by active catalysts as thiswill permit greater productivity.

2. Description of the Prior Art

Organometallics and particularly organo tin compounds such as tinethylhexanoate, tin isooctoate, tin napthenate, di-n-butyl tindilaurate; dibutyl tin diacetate, and tertiary nitrogen tin compoundssuch as dibutyl-tin-di(pyridine-4-carboxylic acid esters) as shown inU.S. Pat. No. 3,595,734; and U.S. Pat. No. 3,164,557 have been used tocatalyze urethane reactions.

Amine compounds and particularly tertiary amines or their salts havebeen used as catalysts for polyurethanes. Examples of amines which aresuited for catalyzing polyurethane reactions are dimethyl benzylamine,triethylenediamine, trimethylamine; alkanolamines such asdiethanolamine, triethanolamine, N-diethyl-ethanolamine; N-hydroxyalkylsubstituted imidazoles and N-vinyl pyrrolidone as shown in U.S. Pat.Nos. 3,645,927; 3,450,648; 3,448,065 and 3,746,663.

U.S. Pat. Nos. 3,620,986 and 3,580,868 show that Mannich bases ofsecondary amines and phenols can be used for catalyzing anisocyanate-hydroxyl reaction. Generally, some aminoalcohol is presentand the phenol radical may contain an active hydrogen atom, e.g. COOH,CONH₂, OH, etc., which can condense into the urethane structure.Typically, these Mannich bases are formed by reacting dimethylamine,formaldehyde, aminoalcohol and a phenol, e.g. Bisphenol A, or salicylicacid amide.

Although the above references indicate the compositions have catalyticactivity, a number of references have suggested similar but differentcompositions as being useful as delayed action catalysts (DAC), i.e.those which initially delay and then catalyze the isocyanate-hydroxylreaction. For example, chelating agents, e.g. beta-diketones and betacarbonyls with aminefree organometallics have been used. Examples ofbeta-diketones useful as a delayed action catalyst in polyurethanechemistry include 2,4-hexanedione, acetylacetone, 1,cyclohexyl-1, 3butanedione; beta-hydroxy ketones, e.g. beta hydroxy quinoline,1hydroxy-9-fluorenone, and alpha-hydroxy ketones, e.g. benzoin, acetoinand others as shown in U.S. pat. No. 3,635,906.

Another example of a delayed action catalyst for the preparation offoamed polyurethane resins is shown in U.S. Pat. 2,932,621. This patentdiscloses that amine salts of dicarboxylic acids and notably the hydroxytertiary amine salts of oxalic acid are particulary effective indelaying the initial reaction between an isocyanate and hydroxyl group,but after an appropriate lapse of time, they become fully effective andcause the reaction to proceed to completion smoothly, rapidly andefficiently.

It has also been proposed to use quaternary ammonium salts of Mannichbases as a delayed action catalyst for the reaction between anisocyanate and polyol to form polyurethanes. Initially, the quaternaryammonium salt has little catalytic effect, but during the reaction itdecomposes to form tertiary amine which can assist in catalyzing thereaction. Examples of quaternary ammonium salts of Mannich bases areshown in U.S. Pat. No. 2,950,262 and are prepared by reacting asecondary amine with an aldehyde and a ketone such as cyclohexanone andthen reacting the Mannich base with an organic halide to form thequaternary ammonium salt.

SUMMARY OF THE INVENTION

This invention relates to amine salts of tertiary amino acids. Theseamine salts are represented by the formula ##STR1##

wherein R₁ and R₂ independently are hydrogen (wherein only one of R₁ orR₂ is hydrogen at a time) alkyl and substituted alkyl groups having from1 to 15 carbon atoms, lower alkanol groups having from 2 to 4 carbonatoms, or combined to form a piperidine, piperizine, morpholine,imidazole or imidazoline radical or substituted radical thereof;

wherein R₃ and R₄ independently are alkylene groups having from 1-6atoms, aralkylene groups with the alkylene portion having from 1 to 6carbon atoms, substituted alkylene and substituted aralkylene groups;

wherein R₅ is hydrogen, a lower alkyl group having from 1 to 6 carbonatoms, an alkenyl group having from 2 to 6 carbon atoms, an aryl groupand substituted derivatives, a cycloaliphatic or alkyl substitutedcycloaliphatic group with the alkyl portion having from 1 to 6 carbons,or a keto alkyl group with the alkyl portion having from 1-6 carbonatoms;

wherein R₆ is hydrogen, or a radical selected from the group consistingof alkyl, phenyl, furfuryl, napthyl, and substituted derivatives of suchgroups;

wherein X is an amine salt of a carboxylic acid group;

wherein Y is a carboxylic acid group, a nitrile group, or an amine saltof an acid group;

wherein m and o independently are 0 or 1;

wherein q is 0 or 1;

wherein p is 1 or 2;

wherein s is 0 or 1; and

wherein p + q + s is 3.

Advantages of the amine of tertiary amino acid catalysts of thisinvention include:

the ability to delay, as compared to conventional amine catalysts, theinitial reaction between an isocyanate and an active hydrogen containingcompound in the formation of a polyurethane;

the ability to catalyze the reaction between an isocyanate and an activehydrogen containing compound;

the ability to form an organometallic catalyzed polyurethane moldingcomposition having excellent flow during initial stages by extending thecream and gelation time and yet end up with a desirable rise and curetime which often is close to those obtained with conventional catalystcompositions; and

the ability, by virtue of being thermally sensitive, to generateadditional reactive amine for catalyzing and enhancing the cure rate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Broadly, the amine salts of the tertiary amino acids of this inventioncan be visualized as amine salts of Mannich type tertiary amino acidadducts having at least monofunctionality in terms of tertiary amine,and at least monofunctionality and preferably at least difunctionalityin the form of an amine salt.

The Mannich type tertiary amino acid adducts typically are formed byreacting a primary and preferably a secondary amine with an aldehydehaving sufficient capability to react with the amine hydrogen and form aterminal methylol group and an organic compound having a hydrogen atomsufficiently reactive to undergo the Mannich addition, and havingpendent acid functionality or functionality which can be converted tothe acid form and then reacting the thus formed Mannich tertiary aminoacid adduct with an amine to form the salt. Further description of thepreparation of the Mannich adduct and type can be found in copendingapplication having U.S. Ser. No. 717,579, and a filing date of Aug. 26,1976, now Pat. No. 4,086,213, and is incorporated by reference.

In preparing the Mannich type adducts described, suitable aminesgenerally are lower alkyl amines having from 1 to 15 carbon atoms, andpreferably 1 to 3 carbon atoms, lower alkanol amines where the alkanolportion has from 2 to 4 carbon atoms; phenyl amines such as mono anddibenzylamine, cyclic amines such as cyclohexylamine anddicyclohexylamine; piperidine; piperizine; imidazole; aralkylene amines,e.g. ethylbenzylamines; heterocyclic amines, e.g. morpholine. The aminescan be substituted with various functional groups, e.g. alkyl, alkoxy,ether and hydroxyl so long as the funtionality does not interfere withthe reaction or impart an adverse characteristic to the resultingpolyurethane resin. The preferred substituted group is a hydroxyl groupas it does not interfere with the reaction and tends to aid the delay inthe initial urethane reaction and thereby lengthen the cream time. Thoseamines best suited for forming the Mannich type are morpholine,diethanolamine, ethanolamine, piperidine and piperizine.

The second component used in forming the Mannich adduct is an aldehyde.Aldehydes and substituted aldehydes useful in forming the Mannichadducts are well known and can be used here. As taught in the art, thesealdehydes must have a pendant aldehyde group which is sufficientlyreactive to form the Mannich adduct. Typically, these aldehydes areactivated, as for example, by an unsaturated group in conjugatedrelationship with the carbonyl aldehyde. Examples of aldehydes bestsuited for practicing the invention are formaldehyde, benzaldehyde,furfuraldehyde, napthaldehyde, and substituted aldehydes such asnitrobenzaldehyde, nitrofurfural, cyanofurfuraldehyde and the like. Forreasons of efficiency and economy, formaldehyde is the preferredaldehyde used in forming the adduct.

The remaining component necessary for forming the Mannich adduct is anorganic compound having at least one hydrogen atom sufficiently reactivefor undergoing a Mannich reaction. Generally in such compounds, thehydrogen atom is positioned on a methylene group alpha positioned to acarbonyl group such as a ketone, a carboxylic acid ester or an acidgroup. Further, the organic compound should have a pendant carboxylicacid or nitrile group or a structure, e.g. ketone or ester which permitsthe formation of a carboxylic acid. The acid then can be neutralizedwith amine and converted to the salt. Examples of organic compoundshaving at least one active hydrogen atom, and in some instances, twoactive hydrogen atoms suited for practicing the invention includedisubstituted saturated acids such as malonic acid, benzyl malonic acid,lower alkyl (C₁ -C₃) malonic acids, furfuryl malonic acid, alkenylmalonic acids, e.g. allyl malonic acid; cyanoacetic acid and keto acids,e.g. 2 ketobutyric acid.

The amine salts of this invention can be formed by reacting the aminoacids with amines such as ethanolamine, diethanolamine, triethanolamine,tri-n-propanolamine, methylamine, ethylamine, propylamine, benzylamine,triethylamine, cyclohexylamine, etc. Highly reactive tertiary aminessuch as bis-(dimethylaminoethyl) ether and triethylenediamine can alsobe used to form the amine salts and these catalysts are particularlyeffective for enhancing the rate of the urethane reaction. Generally,the less active amines, such as ethanol and diethanol amine result inproducing a less active catalyst. Because the tertiary amine is tied tothe Mannich adduct, though, the cream time is lengthened substantiallyover that which is obtained by using tertiary amine alone.

Examples of amine salts of Mannich type adducts include:bis-tri-n-propanolamine salt of bis(hydroxyethylamino) methyl malonicacid, diethanolamine salt of hydroxyethylamino methyl malonic acid,monomethylamine salt of bis(hydroxyethylamino) furfuryl malonic acid,bis-triethylenediamine salt of bis(hydroxyethylamino) benzyl malonicacid, bis-triethylenediamine salt of morpholino benzyl malonic acid,bis-dimethylamine salt of morpholino methyl malonic acid, methylaminesalt of bis(piperidinylmethyl) acetic acid, bis-tri-n-propanolamine saltof diglycolamino methyl malonic acid, propanolamine salt ofbis(piperdinylmethyl) acetic acid, triethanolamine salt of bis(imidazolomethyl) acetic acid, bis-trimethylamine salt of piperidinyl methylmalonic acid and triethylenediamine salt of morpholino benzylcyanoacetic acid.

The amine salts of the tertiary amino acids of this invention can beutilized with other conventional polyurethane catalysts withoutdetracting from the overall benefits. A conventional catalyst that isquite acceptable as a cocatalyst is an organometallic, suitably anorgano tin composition such as dibutyl tin dilaurate, dibutyl tindiacetate, diethyl tin diacetate, dihexyl tin diacetate, stannousoctoate, stannous decanoate and dioctyl tin oxide.

Representative polyisocyanates suited for producing polyurethanes inpracticing this invention are the aliphatic and aromatic polyvalentisocyanates. Examples of aliphatic isocyanates include alkylenediisocyanates such as tri, tetra and hexamethylene diisocyanates;arylene diisocyanates and their alkylation products such as phenylenediisocyanate, napthylene diisocyanate, diphenylmethane diisocyanate,toluene diisocyanate, di and triisopropyl benzene diisocyanate andtriphenylmethane triisocyanates; triesters orisocyanato-phenyl-triphosphoric acid; triesters of para-isocyanatophenyl phosphoric acid; aralkyl diisocyanates such as 1-(isocyanatophenol-ethyl) isocyanate or xylene diisocyanate.

Suitable reactive Zerewitinoff compounds, e.g. polyols for forming thepolyurethanes include aliphatic polyether polyols prepared from thereaction of ethylene or propylene oxides or mixtures thereof with aglycol; glycols such as ethylene glycol, propylene glycol, butyleneglycol, tetramethylene glycol, hexamethylene glycol, and triols such asglycerol, trimethylolpropane, trimethylol ethane, and higher polyolssuch as pentaerythritol, sorbitol, castor oil, polyvinyl alcohol,sucrose, dextrose, methyl glycoside and the like; amino polyols made bythe condensation of alkylene oxides and alkanol amines such astetrahydroxyethylenediamine, tetrahydroxypropyl ethylenediamine; otherorganic compounds having an active hydrogen atom are amines such astriethanolamine, methylamine, diethanolamine, phenylenediamine,tolylenediamine, piperizine and the like.

The polyols also can be incorporated into a polymer and reacted with theisocyanates as in the case of polyesters. A polyester, as is known, isprepared by the reaction between a dicarboxylic acid and a polyol, e.g.a glycol. Examples of conventional dicarboxylic acids suited formanufacturing polyester polyols include succinic, glutaric, adipic,sebacic, phthallic, terephthallic, maleic, fumaric, itaconic,citraconic, and the like. Glycols include, ethylene glycol, propyleneglycol and butylene glycol.

In the preparation of polyurethanes, conventional additives can beutilized for their desired effect without departing or detracting fromthe advantageous aspects of the catalysts of this invention. Forexample, blowing agents such as water or a volatile organic such asdichlorodifluoromethane, dichlorofluoromethane,trichloromonofluoromethane, dichlorofluoromethane,difluorodichloroethane, methylene chloride, carbontetrachloride, butane,pentane, and the like.

Foam stabilizers or surfactants are other additives which can be addedfor enhancing the retention of gas generated during the polymerizationreaction and such stabilizers include silicone block polymers comprisingpolyalkylene glycol units, n-vinyl pyrrolidone, or n-vinylpyrrolidone-dibutyl maleic copolymers or n-vinyl pyrrolidone-dibutylmaleate (vinyl acetate). Other examples are shown in U.S. Pat. No.3,746,663.

In preparing the polyurethanes, the amine salt of a Mannich acid adductis added to the urethane composition in at least a sufficient oreffective proportion for enhancing the cure rate of the urethane. Whenthe catalyst is used alone, generally from about 0.1 to about 5 parts byweight per 100 parts and preferably about 0.5 to about 1.5 per 100 partsby weight of reactive Zerewitinoff hydrogen compound, e.g. polyol areincluded. When less than about 0.1 parts are added to the composition,the catalyst is not present in sufficient proportion to substantiallyinfluence the cure rate of the polyurethane. When more than about 3.5parts catalyst are added to the urethane composition, too much amine maybe introduced and amine odor may be observed. For reasons of economy,the catalyst concentration is preferably from about 0.5 to about 1.5parts.

Often where the organo portion of the amine salt of tertiary amino acidis relatively small or negated by the fact that a hydroxyl or otherpolar group is present, it may be necessary to use a solvent to dispersethe catalyst in the urethane syrup. Virtually any solvent may be usedwhich does not compete with the isocyanate-active hydrogen to form apolyurethane, or does not adversely affect the resultant polyurethane.Conventional solvents such as glycols, e.g. propylene glycol, ethyleneglycol, dipropylene glycol; ethylene carbonate, and amino-nitrilecompositions such as cyanoethyldiethanolamine, which is also a catalyst,can be used as a solvent.

Organometallic catalysts may be included in polyurethane manufacturealong with the amine salts in a proportion of from about 0.005 to about0.5, and preferably 0.01 to 0.2 parts by weight per 100 parts of activeZerewitinoff hydrogen compound. Variations within this broad range arepracticed depending on whether, for example, high and low densitypolyurethanes are prepared and seems to be no significant enhancement ofcatalytic activity or of other desired features to warrant theadditional expenditure and usage of the catalyst.

The following examples are provided to illustrate preferred embodimentsin the invention and are not intended to restrict the scope thereof. Allparts are parts by weight, all percentages are expressed as weightpercentages, and all temperatures are in ° C. unless otherwisespecified.

EXAMPLE 1

Bis-(hydroxyethyl) amino benzyl malonic acid was prepared conventionallyin a flask equipped with a stirrer and reflux condenser by firstcharging 0.1 mol of malonic acid, 0.1 mol of diethanol amine and 100 ccmethanol. The contents were warmed to a temperature of about 20° C. andthen 0.1 mol benzaldehyde were added to the flask and the reactioncommenced. After refluxing the reaction mixture for 1 hour, the methanolwas removed from the reaction mixture by coupling the flask to a vacuumsource and heating to a temperature of about 50° C. The residueremaining in the flask then was triturated in acetone and the resultingacid isolated by filtration.

The bis-triethylenediamine salt of the acid was prepared by mixing 0.1 mof the methanolic solution of the acid with 0.2 m triethylene diamine atroom temperature (25° C.) for 30 minutes, after which the methanol wasremoved under reduced pressure.

EXAMPLE 2

Morpholino benzyl cyanoacetic acid was prepared in the same manner asthe acid of Example 1 except that morpholine was substituted fordiethanolamine and cyanoacetic acid for malonic acid. Themonotriethylenediamine salt of the cyanoacetic acid adduct was preparedin the same manner as the amine salt of Example 1.

EXAMPLE 3

Approximately 100 cc of water and 0.2 mols (21.1 grams) of malonic acidand 0.4 mols (27.4 grams) of imidazole were charged to a round bottomflask. Then 0.4 mols formaldehyde as a 35% aqueous solution were addedover a period of time to the mixture of water, malonic acid andimidazole. The resulting mixture was stirred for about 36 hours at 25°C. after which the contents were heated to a temperature of 50° C. andthe water removed by vacuum. The resulting product was bis-(imidazolemethyl) acetic acid.

EXAMPLE 4

Approximately 100 cc of methanol, 0.1 mols of malonic acid, 0.1 mols ofdiethanolamine, and 0.1 mols of furfuraldehyde were charged to a roundbottom flask. The contents were refluxed for two hours, and then themethanol removed by evacuation. The product obtained wasbis-(hydroxyethyl) furfuryl malonic acid.

The triethylenediamine salt of the above product is prepared in the sameprocedure as the composition in Example 1.

EXAMPLE 5

Conventional high density rigid polyurethane foams were prepared fromthe basic formulation below in conventional manner. In preparing thesepolyurethane foams, the catalyst, comprising an amine salt of a Mannichadduct (as indicated), and organometallic (as indicated) and theconcentration of each catalyst component were varied to determine theoverall effect on the foam formulation. The polyurethane foams wereevaluated for cream time, gelation time, and cure time.

The components used for preparing the high density foam were as follows:

    ______________________________________                                        Component          Amount, parts by weight                                    ______________________________________                                        Mondur® MR Isocyanate                                                                        100                                                        NIAX® DAS-361 Polyol                                                                         65                                                         Thanol® G-400 Polyol                                                                         27.7                                                       Polylite® 34-400 Polyol                                                                      5.0                                                        Water              0.6                                                        DC-193             0.8                                                        Tertiary amino acid or nitrile                                                                   0.5 - 1.5                                                   catalyst parts/100 parts                                                      polyol (php)                                                                 Organometallic catalyst                                                                          0.005 - 0.5                                                 parts/100 parts polyol (php)                                                 ______________________________________                                    

(1) Mondur MR Isocyanate is crude 4,4'methylene bisphenylisocyanatehaving an isocyanate equivalent of about 133, a functionality of about2.7-2.9 and a viscosity of about 150-250 cps.

(2) NIAX DAS-361 Polyol is a sucrose/amine polyol having a hydroxylnumber of 360.

(3) Thanol G-400 Polyol is a glycerol polyol having a hydroxyl number of400.

(4) Polylite 34-400 Polyol is an amino polyol having a hydroxyl numberof 790.

(5) In the examples to follow where a previous example is given, as thecatalyst used but a different amine indicated as a solvent, that aminewas used in place of the particular amine in the previous example; TEDArefers to triethylenediamine; DEA refers to diethanolamine; DPG refersto dipropylene glycol; PG refers to propylene glycol; T-12 refers todibutyl tin dilaurate, php refers to the parts of catalyst (includingsolvent if used) per 100 parts polyol.

The results of the formulation testing is set forth in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    HIGH DENSITY RIGID FOAM                                                                                             Tack Free                               Catalyst        Organometallic                                                                         Cream Time                                                                           Gel Time                                                                            Cure Time                               php      Solvent                                                                              php      Sec.   Sec.  Sec.                                    __________________________________________________________________________    Ex. 1 (0.5)                                                                            (neat) --       61     132   176                                     Ex. 1 (0.7)                                                                            (neat) --       53     113   160                                     Ex. 1 (1.0)                                                                            (neat) --       44     93    125                                     Ex. 1 (0.5)                                                                            (neat) T-12 (0.03)                                                                            48     77    86                                      Ex. 1 (1.0)                                                                            (neat) T-12 (0.03)                                                                            43     69    79                                      Ex. 1 (0.5)                                                                            (neat) T-12 (0.04)                                                                            46     71    78                                      Ex. 1 (1.0)                                                                            (neat) T-12 (0.04)                                                                            40     64    72                                      Ex. 1 (0.5)                                                                            (neat) T-12 (0.05)                                                                            44     63    69                                      Ex. 1 (1.0)                                                                            (neat) T-12 (0.05)                                                                            37     61    65                                      Ex. 2 (0.5)                                                                            (50% DPG)                                                                            --       75     157   227                                     Ex. 2 (1.5)                                                                            (50% DPG)                                                                            --       50     107   154                                     Ex. 2 (0.5)                                                                            (50% DPG)                                                                            T-12 (0.01)                                                                            53     100   125                                     Ex. 2 (1.5)                                                                            (50% DPG)                                                                            T-12 (0.01)                                                                            43     82    105                                     Ex. 2 (1.5)                                                                            (50% DPG)                                                                            T-12 (0.03)                                                                            33     90    111                                     ethylene diamine         60     197   >6 min.                                 (0.4)                                                                         diethanolamine           68     244   >6 min.                                 (0.4)                                                                         diethylenetri-           59     228   > 6 min.                                amine (0.4)                                                                   n-butylamine             61     244   >6 min.                                 TEDA (0.23)                                                                            67% DPG                                                                              --       34     81    106                                     --       --     t-12 (0.04)                                                                            44     78    87                                      --       --T-12 (0.03)                                                                        46       82     94                                            --       --     T-12 (0.05)                                                                            33     61    68                                      __________________________________________________________________________

EXAMPLE 6

Conventional low density rigid polyurethane foam formulations utilizingthe components set forth below were prepared in conventional manner. Inthese polyurethane foams, the catalysts comprising an amino acid andorganometallic and the concentration were varied. The basic formulationused for the low density rigid polyurethane foam was as follows:

    ______________________________________                                        Component          Amount, parts                                              ______________________________________                                        Hylene® TIC.sup.(1)                                                                          105                                                        RS-6406 Polyol.sup.(2)                                                                           109                                                        DC193.sup.(3) Surfactant                                                                         1.5                                                        R11.sup.(4) Blowing Agent                                                                        47                                                         ______________________________________                                    

(1) Hylene TIC is an undistilled, technical grade of tolylenediisocyanate typically having an isocyanate content of 38.75 to 39.75%,an amine equivalent of 105.5 to 108 and a viscosity at 25° C. of 15 to75 cps.

(2) RS-6406 Polyol is a sucrose/amine polyol having a hydroxyl number475.

(3) DC-193 Surfactants are polysiloxane polyoxalkylene block copolymers.Examples are shown in U.S. Pat. Nos. 2,834,748 and 2,917,480.

(4) R-11 Blowing Agent is trichloromonofluoromethane.

(5) See the excerpt for high density formulations for an explanation ofterms used on page 20, paragraph (5). The results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    LOW DENSITY RIGID FOAM                                                                                           Tack Free                                  Catalyst      Organometallic                                                                        Cream Time                                                                           Gel Time                                                                            Cure Time                                  php     Solvent                                                                             php     Sec.   Sec.  Sec.   Shrinkage                                                                           Friability                    __________________________________________________________________________    dimethylcyclo-                                                                              --      18      77   168    none  none                          hexylamine                                                                    (0.8)                                                                         TEDA (0.17)                                                                           67% DPG                                                                             --      30     106   164    slight                                                                              moderate                      TEDA (0.43)                                                                           67% DPG                                                                             --      11      50    75    none  none                          --            T-12 (0.2)                                                                            38      70    98    moderate                                                                            moderate                      bis-DEA salt of                                                                              T-12 (0.08)                                                                          39     117   230    slight-                                                                             very slight                   malonic acid                              moderate                            (0.05)                                                                        "  (1.0)       T-12 (0.08)                                                                          36     123   237    moderate                                                                            slight                        "  (0.5)      T-12 (0.1)                                                                            37     115   241    moderate                                                                            slight                        "  (1.0)      T-12 (0.1)                                                                            34     117   245    moderate-                                                                           slight                                                                  severe                              mono DEA salt  T-12 (0.08)                                                                          36     114   221    slight-                                                                             very slight                   of malonic acid                           moderate                            (0.5)                                                                         "  (1.0)       T-12 (0.08)                                                                          34     133   259    severe                                                                              slight                        "  (0.5)      T-12 (0.1)                                                                            36     103   187    sight-                                                                              slight                                                                  moderate                            "  (1.0)      T-12 (0.1)                                                                            33     111   208    slight                                                                              slight                        __________________________________________________________________________

EXAMPLE 7

Conventional microcellular polyurethane foam formulations were preparedin the usual manner by mixing

87 parts of CP-4701 polyol,

13 parts of 1,4-butanediol,

1.00 parts of L-5303 Silicone Surfactant and

0.30 parts of water to form a polyol premix.

Then the tertiary amino acid (DAC) and organometallic catalyst wereadded and the type and concentration of each was varied as indicated.

After the catalysts were blended with the premix, 50 parts Mondur MRisocyanate were added to the premix and the resulting syrup poured intoa container and evaluated as indicated in Table 2. Terms used in thetable correspond to Example 5, paragraph (5) for the high densityformulations. In addition

(1) CP-4701 Polyol -- is a polyol made from glycerine and propylene andethylene oxides and is marketed by the Dow Chemical Company, and

(2) L-5303 Silicone -- is a surfactant supplied by Union CarbideCorporation.

                  TABL 3                                                          ______________________________________                                        MICROCELLULAR FOAM                                                                                                    Tack                                                                          Free                                                     Organo-   Cream Gel  Cure                                  Catalyst           metallic  Time  Time Time                                  php     Solvent    php       Sec.  Sec. Sec.                                  ______________________________________                                        TEDA (0.2)                                                                            (66.6% DPG)                                                                              T-12 (0.03)                                                                             27    36    49                                   --                 T-12 (0.25)                                                                             30    35    43                                   Ex. 2 (1.0)                                                                           (50% DPG)  --        272   400  600                                   Ex. 2 (2.0)                                                                           (50% DPG)  --        155   255  320                                   Ex. 2 (0.5)                                                                           (50% DPG)  T-12 (0.04)                                                                             81    100  125                                   Ex. 2 (1.0)                                                                           (50% DPG)  T-12 (0.04)                                                                             72    90   110                                   Ex. 2 (2.0)                                                                           (50% DPG)  T-12 (0.04)                                                                             71    90   105                                   --      --         T-12 (0.04)                                                                              360+ --   --                                    ______________________________________                                    

What is claimed is:
 1. An amine salt of a tertiary amino acidrepresented by the formula: ##STR2## wherein in the formula R₁ and R₂independently are alkyl, hydroxy substituted alkyl groups having from 1to 15 carbon atoms, or lower alkanol groups having from 2 to 4 carbonatoms;wherein R₅ is hydrogen, a lower alkyl group having from 1 to 6carbon atoms, an alkenyl group having from 2 to 6 carbon atoms, an arylgroup, a cycloaliphatic or alkyl substituted cycloaliphatic group withthe alkyl portion having from 1 to 6 carbons, or a keto alkyl group withthe alkyl portion having from 1-6 carbon atoms; wherein R₆ is hydrogen,or a radical selected from the group consisting of alkyl, phenyl, and anapthyl groups; wherein X is an amine salt of a carboxylic acid group;wherein Y is a carboxylic acid group, or an amine salt of a carboxylicacid group; wherein q is 0 or 1; wherein p is 1 or 2; wherein s is 0 or1; and wherein p + q + s is
 3. 2. The amine salt of claim 1 wherein whenR₁ and R₂ are alkyl groups, such alkyl groups have from 1 to 6 carbonatoms.
 3. The amine salt of claim 2 wherein s is
 1. 4. The amine salt ofclaim 3 wherein R₆ is hydrogen, or phenyl.
 5. The amine salt of claim 3wherein p is 2 and q is
 0. 6. The amine salt of claim 3 wherein R₅ ishydrogen, methyl or benzyl.
 7. The amine salt of claim 1 wherein R₁ andR₂ is a lower alkanol group having from 2 to 3 carbon atoms.
 8. Theamine salt of claim 7 wherein Y is an amine salt of a carboxylic acidgroup.
 9. The amine salt of claim 8 wherein X and Y are tertiary aminesalts of carboxylic acids.
 10. The amine salt of claim 9 wherein thetertiary amine salts are selected from the group consisting of trialkylamines having from 1 to 3 carbon atoms, trialkanolamines having from 2to 3 carbon atoms and triethylenediamine.